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WO2002030569A1 - Procede de preparation d'un catalyseur a enveloppe annulaire et son utilisation pour produire de l'acroleine - Google Patents

Procede de preparation d'un catalyseur a enveloppe annulaire et son utilisation pour produire de l'acroleine Download PDF

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Publication number
WO2002030569A1
WO2002030569A1 PCT/EP2001/011643 EP0111643W WO0230569A1 WO 2002030569 A1 WO2002030569 A1 WO 2002030569A1 EP 0111643 W EP0111643 W EP 0111643W WO 0230569 A1 WO0230569 A1 WO 0230569A1
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WO
WIPO (PCT)
Prior art keywords
carrier body
coated
mass
catalyst
carrier
Prior art date
Application number
PCT/EP2001/011643
Other languages
German (de)
English (en)
Inventor
Jochen Petzoldt
Signe Unverricht
Heiko Arnold
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2000149873 external-priority patent/DE10049873A1/de
Priority claimed from DE2000159713 external-priority patent/DE10059713A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2002223606A priority Critical patent/AU2002223606A1/en
Priority to JP2002534002A priority patent/JP4119748B2/ja
Priority to AT01986623T priority patent/ATE268223T1/de
Priority to US10/398,287 priority patent/US7122707B2/en
Priority to DE50102496T priority patent/DE50102496D1/de
Priority to EP01986623A priority patent/EP1333922B1/fr
Publication of WO2002030569A1 publication Critical patent/WO2002030569A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a process for producing a catalyst which consists of a support body and a catalytically active oxide composition of the general formula I applied to the surface of the support body
  • X 3 Li, Na, K, Cs and / or Rb, 0.2 ⁇ a ⁇ 1,
  • the intimate dry mixture is thermally treated at a temperature of 150 to 350 ° C. to obtain a precursor composition, the support body is moistened with water, and then brought into contact with finely divided precursor composition a layer of the precursor mass is attached to the surface of the moistened carrier body, then the coated carrier body is dried and finally the dried carrier body coated with precursor mass is calcined at a temperature of 400 to 600 ° C.
  • the present invention further relates to catalysts which are obtainable by the above processes and their use for the gas-phase catalytic oxidation of propene to acrolein.
  • the production of the important intermediate product acrolein by heterogeneously catalyzed gas phase oxidation of propene is generally known (cf., for example, DE-A 19855913).
  • Acrolein is used inter alia. for the production of acrylic acid, the alkyl esters of which are used in particular as monomers for the production of aqueous polymer dispersions.
  • DE-A 19855913 recommends the use of rings formed exclusively from active multimetal oxides I (full catalyst rings) and the use of active multimetal oxides I (spherical shell catalysts) applied to spherical support bodies as catalysts for the gas-phase catalytically oxidative production of acrolein from propene ,
  • DE-A 4442346 relates to the production of ring-shaped coated catalysts of active multimetal oxide compositions of the general formula I.
  • DE-A 4442346 recommends the use of a solution consisting of 20 to 90% by weight as a liquid binder when applying the active multimetal oxides I. Water and 10 to 80 wt .-% of an organic compound dissolved in water.
  • a disadvantage of the ring-shaped coated catalysts of DE-A 4442346 is that their activity and selectivity with regard to the formation of acrolein when used as catalysts for the gas-phase catalytic partial oxidation of propene is also unsatisfactory.
  • EP-A 900774 also teaches the preparation of coated catalysts whose active mass stoichiometry corresponds to the general formula I.
  • the geometry of the support used to produce the coated catalysts can be any.
  • liquid binders of the most varied types one finally water.
  • only spherical support bodies are used and an aqueous glycerol solution is always used as the binder.
  • shell catalysts produced in EP-A 900774 are recommended as catalysts for the gas-phase catalytic oxidation of propene to acrolein, they are unsatisfactory either in terms of their activity or in terms of their selectivity in the formation of acrolein.
  • DE-A 19948523 ring-shaped coated catalysts are also recommended for the gas-phase catalytic oxidation of propene to acrylic acid, but DE-A 19948523 does not contain any specific processes for their preparation.
  • the object of the present invention was therefore to provide a process for the preparation of a catalyst, consisting of a support body and a catalytically active oxide composition applied to the surface of the support body, by means of which coated catalysts can be obtained which are improved as coated catalysts Activity and increased selectivity of acrolein formation are suitable for the gas-phase catalytic oxidation of propene to acrolein.
  • ⁇ i Co and / or Ni
  • X 2 Si and / or Al
  • X3 Li, Na, K, Cs and / or Rb
  • the intimate dry mixture is thermally treated at a temperature of 150 ° to 350 ° C., preferably 220 to 280 ° C. to obtain a precursor composition, the support body is moistened with water, thereafter, by contacting finely divided precursor mass on the surface of the moistened carrier body, a layer of the precursor mass is attached, then drying the coated carrier body and finally calcining the dried carrier body coated with precursor mass at a temperature of 400 to 600 ° C, which is characterized in that that the support body has ring geometry.
  • the annular support bodies to be used according to the invention are preferably chemically inert, i.e. they essentially do not interfere in the course of the catalytic gas phase oxidation of the propene to acrolein, which is catalyzed by the coated catalysts produced according to the invention.
  • aluminum oxide, silicon dioxide, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide are particularly suitable as materials for the carrier bodies.
  • the surface of the carrier body can be both smooth and rough.
  • the surface of the carrier body is advantageously rough, since an increased surface roughness generally results in an increased adhesive strength of the applied shell on the catalyst precursor composition or on the oxidic active composition.
  • the surface roughness R 2 of the support body is often in the range from 40 to 200 ⁇ m, often in the range from 40 to 100 ⁇ m (determined in accordance with DIN 4768 sheet 1 using a "Hommel Tester for DIN-ISO surface measurement parameters" from Hommel Erke, DE) ,
  • the carrier material can be porous or non-porous.
  • the carrier material is expediently non-porous (total volume of the pores based on the volume of the carrier body ⁇ _ 1% by volume).
  • the length of the carrier rings to be used according to the invention is typically 2 to 10 mm and their outside diameter is typically 4 to 10 mm.
  • the wall thickness of the carrier rings is usually 1 to 4 mm.
  • Carrier ring dimensions suitable according to the invention are also 3 to 6 mm (length), 4 to 8 mm (outer diameter) - and 1 to 2 mm (wall thickness).
  • inventive ring geometry also considered 2 to 4 mm (length), 4 to 8 mm (outer diameter) and 1 to 2 mm (wall thickness).
  • Striking carrier ring geometries according to the invention are e.g. 7 mm x 3 mm x 1.5 mm (outside diameter x length x wall thickness) and 5 mm x 3 mm x 1.5 mm (outside diameter x length x wall thickness).
  • the thickness of the active oxide mass present on the coated catalysts obtainable according to the invention is generally from 10 to 1000 ⁇ . However, it can also be 100 to 700 ⁇ m, 200 to 600 ⁇ m or 300 to 500 ⁇ m. Possible shell thicknesses are also 10 to 500 ⁇ m or 200 to 300 ⁇ m.
  • the fineness of the precursor mass to be applied to the surface of the ring-shaped carrier body is of course adapted to the desired thickness of the active oxide mass shell.
  • a shell thickness of 100 to 500 ⁇ m e.g. Powder from precursor mass, of which at least 50% of the powder particles pass through a sieve with a mesh size of 1 to 10 ⁇ m and whose proportion of particles with a longest dimension above 50 ⁇ is less than 1% (based on the total number of particles).
  • the distribution of the longest dimensions of the powder particles corresponds to a Gaussian distribution due to the manufacturing process.
  • the base-coated carrier body then forms in the subsequent period in the manner according to the invention first to be moistened and then to be coated by contact with dry, finely divided precursor composition, etc.
  • the addition of finely divided precursor composition and binder is generally carried out continuously.
  • the rotating rotary container passes the carrier bodies under two metering devices arranged at a certain distance one after the other.
  • the first of the two metering devices suitably corresponds to a nozzle (for example an atomizer nozzle operated with compressed air) through which the carrier bodies rolling in the rotating turntable are sprayed with water and moistened in a controlled manner.
  • the second metering device is located outside the atomizing cone of the water sprayed in as a binder and serves to supply the finely divided precursor mass (for example via a shaking channel or powder screw).
  • the controlled moistened carrier rings take up the supplied precursor mass powder, which is compacted by the rolling movement on the outer surface of the ring-shaped carrier body to form a coherent shell (such a compacting movement does not take place in the inner circle of the hollow cylindrical carrier body, which is why this in remains essentially uncoated).
  • the base body coated in this way again passes through the spray nozzle in the course of the subsequent rotation, is moistened in a controlled manner in order to be able to take up a further layer of finely divided pre-discharge devices in the course of the further movement, etc. (intermediate drying is generally not necessary).
  • the removal of the binder to be used as water according to the invention can e.g. by supplying heat, e.g. by the action of hot gases such as N or air.
  • drying can also be done in a drying cabinet.
  • the drying temperature is usually 100 to 150 ° C.
  • the method according to the invention brings about a satisfactory adhesion of successive layers to one another and also the base layer on the surface of the carrier body.
  • the moistening of the surface of the carrier body to be coated is carried out in a controlled manner.
  • An advantage of the method according to the invention is that the water used as a binder can be removed in a controlled manner, for example by evaporation. In the simple case, this can be done by exposure to hot gases at the appropriate temperature (usually 100 to 150 ° C). Exposure to hot gases can also only result in predrying. The final drying can then take place, for example, in a drying oven of any kind (for example a belt dryer).
  • An essential feature of the method according to the invention is that it is not the catalytically active oxidic mass as such but rather a precursor mass that is applied to the carrier body.
  • the annular support coated and dried with the precursor composition must be calcined according to the invention in order to produce the catalytically active oxidic composition. This can take place within a period of a few hours (typical calcination times are 2 h to 10 h, the required calcination time decreasing with increasing calcination temperature) at temperatures from 400 to 600 ° C., preferably at temperatures from 430 to 500 ° C.
  • the calcination can be carried out under an oxidizing, under an inert or under a reducing atmosphere. It expediently takes place in air. Of course, it can also be carried out under vacuum.
  • an inert gas atmosphere e.g. inert gases such as molecular nitrogen and / or noble gases such as He, Ar.
  • the calculation can be carried out e.g. done in a forced air oven.
  • the catalyst precursor mass with which the ring-shaped supports are to be coated it is customary to start from sources of the constituents of the catalytically active, oxidic mass which are suitable in a manner known per se and to produce the most intimate, generally finely divided, Dry mixture, which is then thermally treated at a temperature of 150 to 350 ° C, preferably 220 to 280 ° C (usually 1 h to 6 h).
  • This thermal treatment can also take place under an inert, reducing or oxidizing atmosphere. It is usually carried out in air.
  • the precursor mass formed during the thermal treatment, under which the sources used usually decompose, can then be applied to the carrier rings in finely divided form.
  • the sources to be used according to the invention are either already oxides or those compounds which are obtained by heating, at least in the presence of Oxygen that can be converted into oxides.
  • Oxygen that can be converted into oxides.
  • ammonium metallates, halides, nitrates, formates, oxalates, acetates, carbonates or hydroxides are therefore particularly suitable as starting compounds.
  • the intimate mixing of the starting compounds can take place in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and, after mixing and optionally pressing, are thermally treated according to the invention.
  • the intimate mixing is preferably carried out in wet form.
  • the starting compounds are mixed together in the form of an aqueous solution or suspension.
  • the aqueous mass is then dried. Drying is advantageously carried out by spray drying (the gas inlet temperature is generally 280 to 420 ° C. and the gas outlet temperature is typically 100 to 150 ° C.).
  • the powder that arises during spray drying often proves to be too finely divided for immediate further processing. In these cases, it can be kneaded with the addition of water. After kneading, the kneaded material is appropriately roughly divided and dried (e.g. at temperatures of 100 to 150 ° C in a drying cabinet). Drying can then be followed by the thermal treatment according to the invention at 150 to 350 ° C. before the precursor mass obtained for the coating purpose according to the invention, e.g. is converted into the required finely divided form by grinding.
  • shell catalysts whose catalytically active oxide mass has only Co as X 1 .
  • the stoichiometric coefficient b is preferably in the range 4 ⁇ b ⁇ 8, and particularly preferably in the range 6 ⁇ b ⁇ 8.
  • the value for the variable c is advantageously in the range 1 ⁇ c ⁇ 5 and with a particular advantage in the range 2 ⁇ c ⁇ 4.
  • the stoichiometric coefficient e is expediently> 0. Preferably 0.01 e e ⁇ 0.5 and particularly preferably 0.05 ⁇ e ⁇ 0.2.
  • Shell catalysts according to the invention with catalytically active catalysts are favorable Oxide compositions whose molar ratio of Co / Ni is at least 2: 1, preferably at least 3: 1 and particularly preferably at least 4: 1. The best is only Co.
  • the value for 1.5 x (a + c) + b is in the range> 11 and ⁇ 14, preferably in the range> 11.5 and ⁇ 13. Values for 1.5 x (a + c) + b in the range> 11.8 and ⁇ 12.5.
  • coated catalysts according to the invention are suitable according to the invention whose catalytically active oxide mass corresponds to a catalytically active oxide mass specified in DE-A 19855913.
  • coated catalysts obtainable according to the invention are not only suitable for the selective gas phase oxidation of propene to acrolein, but also for the partial gas phase oxidation of other organic compounds (other alkenes, alkanes, alkanones or alkenols) to give ⁇ , ⁇ -unsaturated aldehydes and / or carboxylic acids.
  • the coated catalysts according to the invention are suitable for carrying out the partial gas phase oxidation of propene to acrolein using increased propene loads on the catalyst feed, as is e.g. is described in DE-A 19955168, in DE-A 19948523 and in DE-A 19948248. It is essential that they exhibit increased activity and increased selectivity of acrolein formation even with increased propene load.
  • the aqueous mixture obtained was spray-dried in a spray dryer from Niro (spray dryer Niro A / S Atomizer Transportable Minor System, centrifugal atomizer from Niro, DK).
  • the initial temperature was 60 ° C.
  • the gas inlet temperature was 360 + 10 ° C, the gas outlet temperature was 115 ⁇ 5 ° C.
  • the entire aqueous mixture was conveyed at a rate of 2 l / h over a two-component nozzle with attached atomizer wheel with a spray nozzle pressure of 5.2 bar with air as carrier gas (40m 3 / h) sprayed in cocurrent. After powder separation in a cyclone, a spray powder with a particle size of 20 to 25 ⁇ m was obtained.
  • the kneaded material was roughly divided and dried for 2 hours in a drying cabinet from Binder, DE, type FD 53 (53 1 internal volume) at 120 ° C.
  • the dried kneaded material was thermally treated in a forced-air oven from Nabertherm, DE, type N60 / A (60 l internal volume).
  • the furnace was first heated to 240 ° C. in the course of 2 hours and held at this temperature for 10 minutes. Then within 60 min. heated to 280 ° C. This temperature was kept constant for one hour.
  • a gas stream of 300 Nl / 1 air was passed through the forced air oven throughout the process. A precursor mass A was thus obtained.
  • the solution A 'at 60 ° C. was added to the aqueous solution B ′ at 60 ° C. within 15 minutes. added with stirring via a pump. After the addition had ended, the mixture was stirred at 60 ° C. for a further 5 min. Subsequently, while maintaining the 60 ° C., 205.11 g of silica sol (Ludox-®TM, Du Pont, 50% by weight SiO 2 , density: 1.39 g / ml, pH: 8.8, alkali content ⁇ 0.5 % By weight) was added and the mixture was stirred at 60 ° C. for a further five minutes.
  • silica sol Lidox-®TM, Du Pont, 50% by weight SiO 2 , density: 1.39 g / ml, pH: 8.8, alkali content ⁇ 0.5 % By weight
  • the precursor mass to be used for the coating was ground in a centrifugal mill (type ZM 100, from Retsch, DE) to a grain size> 0 and ⁇ 0.12 mm.
  • the grain size distribution is as follows:
  • X the percentage of grains whose diameter is> D.
  • Y the percentage of grains whose diameter is ⁇ D.
  • An atomizer nozzle operated with compressed air was used for 60 min. about 45 ml of liquid binder sprayed onto the carrier. The nozzle was installed in such a way that the spray cone wetted the carrier bodies in the drum, which were carried by driving plates to the uppermost point of the inclined drum, in the upper half of the rolling path.
  • the finely divided precursor mass was introduced into the drum via a powder screw, the point of the powder additions being within the unrolling section but below the spray cone. Due to the periodic repetition of wetting and powder metering, the base-coated carrier body itself became the carrier body in the following period. After the coating had been completed, the coated carrier body was dried for 2 hours at 120 ° C. in a drying cabinet (company Binder, DE, internal volume 53 l). The dried coated catalyst precursors were then calcined in a forced-air oven from Heraeus, DE (type K 750/2 S, internal volume 55 l) through which air flowed through 800 Nl / h.
  • the convection oven was opened within 210 min. heated linearly from 25 ° C to 470 ° C. This temperature was then maintained for 6 hours.
  • the shell catalysts produced in this way had an active mass layer thickness of 370 + 30 ⁇ m in all cases.
  • Comparative shell catalyst VS1 precursor mass A was used, spheres with a diameter of 2.5 to 3.5 mm were used as the carrier body, the liquid binder was water;
  • Shell catalyst SI according to the invention: as VS1, but hollow cylinders with an outer diameter of 7 mm and a length of
  • Comparative shell catalyst VS2 Like SI, but a 25% by weight solution of glycerol in water was used as the liquid binder;
  • Comparative shell catalyst VS3 Like SI, however, the precursor mass A was not used for the coating, but rather a 6 h at 470 ° C in the above-mentioned circulating air oven (through which 800 Nl / h of air flowed) Heraeus calcined precursor mass A (the heating of the circulating air oven from 25 ° C to 470 ° C within 210 min. by linear temperature increase). The calcination due after the coating of the carrier bodies and drying was omitted.
  • Comparative shell catalyst VS4 Like VS1, but precursor mass B was used as the precursor mass;
  • Shell catalyst S2 according to the invention Like SI, but precursor mass B was used as the precursor mass;
  • Comparison cup catalyst VS5 Like VS2, but the precursor mass B was used as a preliminary discharge. D) Testing the shell catalysts produced under C.
  • the feed length was selected in all cases so that the fixed catalyst bed contained 32 to 34 g of active composition.
  • the entire length of the reaction tube was heated with a salt bath flowing around it.
  • a mixture of 5% by volume of propene, 9.5% by volume of oxygen and 85.5% by volume of nitrogen was used as the reaction gas starting mixture.
  • the load on the reaction tube with the reaction gas starting mixture was in all cases 10 1 / h.
  • the salt bath temperature was set in all cases in such a way that propene conversion U of 95 mol% was achieved in one pass through the reaction tube.
  • the selectivity S of the product of value formation on acrolein was determined by gas chromatographic analysis.
  • the selectivity data are relative selectivity data S R. That is, within the series of shell catalysts VS1, SI, VS2 and VS3, the selectivity of acrolein formation achieved with VS1 was set to 100 and the selectivity of acrolein formation achieved with the other three shell catalysts was based on this.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé permettant la préparation d'un catalyseur à enveloppe annulaire qui est constitué d'un corps de support annulaire et d'une masse oxydique active d'un point de vue catalytique, appliquée à la surface du corps de support contenant au moins du molybdène, du bismuth, du cobalt et/ou du nickel et du fer. D'après ledit procédé, à partir de composés de départ des constituants élémentaires de la masse oxydique active d'un point de vue catalytique, est produit un mélange sec intime, le mélange sec intime est traité thermiquement à une température de 150° à 350 °C pour obtenir une masse de précurseur, le corps de support est humidifié avec de l'eau, puis une couche de la masse de précurseur est fixée grâce à la mise en contact avec de la masse de précurseur à fines particules à la surface du corps de support humidifié, et le corps de support revêtu est finalement séché et le corps de support séché, revêtu de masse de précurseur est calciné à une température allant de 400 ° à 600 °C. Le catalyseur ainsi obtenu convient à l'oxydation catalytique en phase gazeuse d'échantillons pour produire de l'acroléine.
PCT/EP2001/011643 2000-10-10 2001-10-09 Procede de preparation d'un catalyseur a enveloppe annulaire et son utilisation pour produire de l'acroleine WO2002030569A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU2002223606A AU2002223606A1 (en) 2000-10-10 2001-10-09 Method for producing an annular shell catalyst and use thereof for producing acrolein
JP2002534002A JP4119748B2 (ja) 2000-10-10 2001-10-09 環状の殻型触媒の製造方法およびアクロレインを製造するための該触媒の使用
AT01986623T ATE268223T1 (de) 2000-10-10 2001-10-09 Verfahren zur herstellung eines ringförmigen schalenkatalysators und verwendung davon zur herstellung von acrolein
US10/398,287 US7122707B2 (en) 2000-10-10 2001-10-09 Method for producing an annular shell catalyst and use thereof for producing acrolein
DE50102496T DE50102496D1 (de) 2000-10-10 2001-10-09 Verfahren zur herstellung eines ringförmigen schalenkatalysators und verwendung davon zur herstellung von acrolein
EP01986623A EP1333922B1 (fr) 2000-10-10 2001-10-09 Procede de preparation d'un catalyseur a enveloppe annulaire et son utilisation pour produire de l'acroleine

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2000149873 DE10049873A1 (de) 2000-10-10 2000-10-10 Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse
DE10049873.6 2000-10-10
DE2000159713 DE10059713A1 (de) 2000-12-01 2000-12-01 Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse
DE10059713.0 2000-12-01

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WO2002030569A1 true WO2002030569A1 (fr) 2002-04-18

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US (1) US7122707B2 (fr)
EP (1) EP1333922B1 (fr)
JP (1) JP4119748B2 (fr)
CN (1) CN1174807C (fr)
AT (1) ATE268223T1 (fr)
AU (1) AU2002223606A1 (fr)
DE (1) DE50102496D1 (fr)
WO (1) WO2002030569A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7341974B2 (en) 2002-05-16 2008-03-11 Lg Chem, Ltd. Method for preparing a catalyst for partial oxidation of propylene
DE102007025869A1 (de) 2007-06-01 2008-07-03 Basf Se Verfahren der Wiederbeschickung der Reaktionsrohre eines Rohrbündelreaktors mit einem neuen Katalysatorfestbett
DE102007017080A1 (de) 2007-04-10 2008-10-16 Basf Se Verfahren zur Beschickung eines Längsabschnitts eines Kontaktrohres
DE102007028332A1 (de) 2007-06-15 2008-12-18 Basf Se Verfahren zum Beschicken eines Reaktors mit einem Katalysatorfestbett, das wenigstens ringförmige Katalysatorformkörper K umfasst
CN108855095A (zh) * 2018-02-08 2018-11-23 贵州理工学院 甲烷重整多核壳空心型催化剂镍-镍硅酸盐-SiO2的制备方法
CN108889313A (zh) * 2018-06-20 2018-11-27 上海迅凯新材料科技有限公司 一种负载型镍系催化剂及其制备方法和应用

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EP1333922A1 (fr) 2003-08-13
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